Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 10
Showing 1-50 articles out of 69 articles from the selected issue
  • Tomitake Tsukihara, Yukiteru Katsube, Kumiko Fujimori, Toshiaki Ito
    1972 Volume 45 Issue 10 Pages 2959-2963
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of cesium tetrakis(succinimidato) copper(II) dihydrate, Cs2(Cu(sucim)4)·2H2O, has been determined by means of X-ray analysis. The crystals are violet rhombic plates. Dimensions of the triclinic unit cell are a=9.19, b=15.32, c=8.39 Å, α=88.7°, β=92.0°, γ=93.8°, and z=2. The space group is C\bar1. The structure has been determined by the Patterson synthesis, a series of Fourier syntheses and the least-squares method. The coordination around the copper atom is a square planar. Two independent cesium ions have a quite different environment. Complex anions, (Cu(sucim)4)2−, are linked with each other through the hydrogen bonds between water and carboxyl oxygen atoms.
  • Chiyoshi Kamizawa, Hitoshi Masuda, Seiichi Ishizaka
    1972 Volume 45 Issue 10 Pages 2964-2966
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Transport phenomena of some aliphatic amino acids and aminobenzoic acids were investigated with Loeb type membranes annealed at 60–80°C.
    The quantitative relation between permeability through the membrane and dissociation of amino acid was examined. The charged species are rich in the solutions of amino acids such as L-leucine, L-alanine, and L-glutamic acid, regardless of the pH of solution, thus making the rejection by membranes large; the rejection of L-leucine which had a rejection of 35% for NaCl, was 63.2% even for the membrane cured at 60°C. On the other hand, for aminobenzoic acids, the number of uncharged species in solution varied with the change in pH, and the rejection varied with pH. The fluxes of aminobenzoic acids were in linear relation to the calculated amount of uncharged species. The results of adsorption experiments indicate that the amounts of adsorbed aminobenzoic acid to cellulose acetate were in logarithmic relation to calculated amounts of undissociated species. The results support the view that dissociated species are more difficult to be distributed in membrane than undissociated ones.
  • Chiyoshi Kamizawa, Seiichi Ishizaka
    1972 Volume 45 Issue 10 Pages 2967-2969
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Transport phenomena of some surfactants were investigated with Loeb-type skinned membranes annealed at 60, 70, 75, and 80°C, with the following results. (1) The rejection of cationic and anionic surfactants is larger than that of nonionic surfactants, especially at concentrations below CMC. (2) In the case of nonionic surfactants, their fluxes decrease with the increase of molecular weight. (3) The effect of CMC on the transport of surfactants is great, particulary in the case of nonionic surfactants. (4) Concentration polarization on the surface of the membrane can be predicted by taking into account the difference between surfactant fluxes below and above CMC.
  • Masao Kakimoto, Tsunetake Fujiyama
    1972 Volume 45 Issue 10 Pages 2970-2974
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The shapes and intensities of the fundamental bands, v2 (the CSC bending) and v3 (the C–S antisymmetric stretching), were measured for liquid carbon disulfide and its chloroform solutions. The intensity data were corrected for the effect of the dielectric field at each frequency. The analyses of the v2 and v3 bands indicate that the band-widths of liquid carbon disulfide can not be explained only in terms of reorientational relaxation. It is also shown that the vibrational relaxation of the resonance type can well explain the concentration dependence of the observed band-widths. The magnitudes of the vibrational and reorientational relaxations obtained from the bandshape analyses are given. It is emphasized that the measurement of the absolute intensity is indispensable for the analyses of the infrared-band shapes of condensed phases.
  • Kasumi Ikegami, Mitsuo Ito
    1972 Volume 45 Issue 10 Pages 2974-2976
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The polarized phosphorescence spectra of quinoxaline in durene and p-dimethoxybenzene host crystals were observed at 4.2°K, and the vibronic bands of the phosphorescence spectrum were assigned. It was found that the intensity of vibronic bands polarized along long molecular axis arises from the vibronic spin-orbit coupling routes
    (Remark: Graphics omitted.)
    and the intensity of vibronic bands polarized along short molecular axis from the routes
    (Remark: Graphics omitted.)
    It was concluded that all the vibronic phosphorescence bands of quinoxaline originate from the Tz zero-field sublevel. This is in line with the results of El-Sayed and Brewer deduced from the magnetic field effect on the phosphorescence spectrum.
  • Yoshinori Sasaki, Shiro Ueda
    1972 Volume 45 Issue 10 Pages 2977-2983
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The phosphidation kinetics of a copper exposed to a phosphorus atmosphere from 1 to 10 Torr absolute pressure in the temperature range of 150–250°C have been determined with a closed system. The reaction rate in the earlier periods of time was linear and, subsequently, parabolic; therefore, it can be considered that the rate-determining process changes from adsorption to diffusion. The linear rate constants were expressed as a function of the phosphorus pressure on the basis of the Langmuir adsorption isotherm. The P4 molecule is chemically adsorbed as two —P=P—, whereas at higher temperatures and pressures the solubility process appears to be predominant. From the phosphorus distribution in cross sections of scaling films, it has been revealed that, in the adsorptoincontrolled regions, the phosphorus content is maintained at a constant concentration, corresponding to Cu3P, and that, in the diffusion-controlled regions, solid solutions more rich in phosphorus than Cu3P are formed at the outer layers. The faceted crystals of Cu3P have sometimes developed with an orientation of the (300) plane, depending on the reaction conditions.
  • Yasumichi Oishi, Masayasu Sugisaki, Yoshinobu Kamei, Yasuyuki Shono
    1972 Volume 45 Issue 10 Pages 2984-2988
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Self-diffusion coefficients of CO2 of the binary system of Ne and CO2 were measured for the whole composition range at 25°C under 760 mmHg. The system was also analysed as a ternary system of 20Ne, 22Ne, and CO2. The isotope separation of 20Ne and 22Ne during the course of diffusion was measured and analyzed by means of the ternary diffusion equations obtained by an extension of Darken’s binary diffusion equation. The experimentally observed 22Ne/20Ne ratios agreed well with the values calculated by the equations. The results show that the concept of the intrinsic diffusion flux density, introduced by Darken for binary diffusion, is valid and applicable to ternary diffusion in the gaseous system.
  • Mikio Hoshino, Shigeya Niizuma, Masao Koizumi
    1972 Volume 45 Issue 10 Pages 2988-2992
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that the photoreduction of acridine in cyclohexane and toluene occurs via molecular and radical mechanisms. The T-energy transfer experiments using biacetyl as an energy acceptor have revealed that the molecular mechanism occurs in the T(n–π*) state, and the radical in the singlet excited state. The effect of the addition of piperylene on the quantum yield of photoreduction was investigated in cyclohexane, methanol, ethanol and isopropanol. The results have been interpreted on the following assumptions. 1) Complete T-energy transfer from acridine to piperylene. 2) No quenching action of piperylene on the singlet excited acridine. 3) Complete transformation of C-radicals of acridine to stable products by piperylene. The results have led to the conclusion that the C-radical undergoes disproportionation in cyclohexane, methanol and ethanol, while it is completely transformed to an acridan-type compound in isopropanol.
  • Ralph J. Tykodi
    1972 Volume 45 Issue 10 Pages 2993-2997
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The proper correlation of thermodynamic quantities derived from experimental gas-solid adsorption systems with those derived from statistical mechanical models is discussed; the usual method of making the correlation is found to be unsatisfactory, and a new method is proposed.
  • Yoshio Takasu, Toshiro Yamashina
    1972 Volume 45 Issue 10 Pages 2997-3002
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The catalytic activities of nine copper-nickel alloys (5 cm2 in area) in hydrogen-deuterium exchange were examined at 1.5 Torr partial pressures of hydrogen and deuterium, using an ultra-high vacuum apparatus incorporated with an omegatron mass spectrometer for continuous gas analysis. Without any surface treatment, the activity was greatest on pure nickel, decreased gradually as the content of copper in the alloys increased and virturally vanished in the alloys containing copper more than 70%. The activity of each alloy sample was observed to be extremely enhanced by a slight surface treatment of oxidation-reduction (Po2=2.3 Torr at 500°C for 1 min, PH2=16 Torr at 300°C for 2 hr). The activity of the 85% copper alloy after the oxidation-reduction treatment was greatest, one hundred times that of pure nickel. Annealing for a short time in an ultra-high vacuum subsequent to the oxidation-reduction treatment caused the catalytic activity to decrease abruptly at a critical temperature (425°C). On the bases of the electron microscopic observations and the measurement of the surface roughness changed by the pre-treatments, the nature of active sites on copper-nickel alloys was discussed.
  • Masamoto Iwaizumi, Takashi Matsuzaki, Taro Isobe
    1972 Volume 45 Issue 10 Pages 3002-3005
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The ESR of the 4-phenyl-1,3-dioxane anion shows a line-width alternation effect which can be attributed to the restricted rotation between the 1,3-dioxane and benzene rings. From the temperature dependence of the line-width alternation effect, the activation energy was determined to be 180±110 cal·mol−1. The preferential conformation between the two rings was estimated from the hyperfine splitting constant of the proton at the 4 position in the 1,3-dioxane ring, to be that where the two rings have some angle close to 90° rather than the structure where they are parallel. It was also found that an odd electron, which mainly occupies a vacant π orbital in the benzene ring, delocalizes appreciably into a part of the 1,3-dioxane ring.
  • Makoto Ghikira, Taro Isobe
    1972 Volume 45 Issue 10 Pages 3006-3011
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It has been concluded, from computer simulations of the observed ESR line shapes, that the dimeric structure of bis- (N-salicylidenemethylaminato)copper(II) in a frozen toluene solution is similar to that in its γ-form crystals. Furthermore, the difference between the hyperfine splittings observed at both edges of the triplet spectra for ΔM=1, the large frequency dependence of the fine-structure splitting, and the additional hyperfine structures observed in the field range between the so-called low-field parallel and perpendicular lines have been found to be due to the noncoincidence of the principal axes of the g tensor with those of the fine-structure tensor.
  • Seiichiro Higuchi, Eisaku Kuno, Shigeyuki Tanaka, Hitoshi Kamada
    1972 Volume 45 Issue 10 Pages 3011-3016
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared absorption intensities of out-of-plane CH bending and ring out-of-plane deformation vibrations of aniline have been measured in an acetone solvent mixed with various quantities of acetic acid. When such solvents are used, new peaks attributable to aniline interacting with the acid appear as shoulders of each of the original bands. A marked decrease in the sums of the intensities of the above two modes (Ao) has been observed for the bands of aniline interacting with the acid. It is demonstrated that the degree of such a decrease in intensity depends on the molar ratios of aniline and the acid. When there exists enough the acid in comparison with aniline, the values of Ao become minimum. On the other hand, when the numbers of the exsiting acetic acid molecules are much smaller than those of aniline, the values of Ao are considerably greater than those in the former case. In this case, a farily long time is needed until the interaction reaches an equilibrium state. Finally, when a very large amount of the acid is added, the bands attributable to aniline interacting with the acid are no longer observed. An attempt has been made to interpret these phenomena in terms of the state of the aggregation of aniline, acid and acetone molecules in the solutions.
  • Tsunetake Fujiyama
    1972 Volume 45 Issue 10 Pages 3016-3020
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The vibration spectra of liquid n-butyl chloride and n-butyl bromide are observed in the region of 1500–100 cm−1. From the analyses of spectra corresponding to the skeletal deformation vibrations, the molecular configurations are determined for both molecules. All the possible rotational isomers, the TT, GT, TG, GG, and GG′ forms, are observed for n-butyl chloride, while four isomers, the TT, GT, TG, and GG forms, are observed for n-butyl bromide. The results are compared with those of the electron-diffraction methods. It is shown that unfamiliar interactions must be considered for the parallel (1:3) interaction between methyl and chlorine substituents.
  • Masao Kakimoto, Tsunetake Fujiyama
    1972 Volume 45 Issue 10 Pages 3021-3026
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The shapes and intensities of the fundamental bands of liquid methyl cyanide were observed by conventional transmittance method. Using the refractive indices observed by the ATR method, the observed absorption indices were corrected for the dielectric-field effect. The band shapes were analyzed from the point of view of moment analysis or correlation-function analysis. The results indicate that the shapes of a1-type vibrations are good Lorentzian shapes, while those of the e-type can be explained as superpositions of Lorentzian and Gaussian functions. It is also found that the band-widths of the e-type vibrations were quite different from each other. Taking into account the effect of vibration-rotation interaction on the band-widths, the disagreement could be explained well. From the analyses of the band shapes of ν7 and nu8, the life-time function, ψ(t), was obtained; it represents the decay of the fraction of freely-rotating molecules.
  • Naoto Ohmichi, Akio Tajiri, Takeshi Nakajima
    1972 Volume 45 Issue 10 Pages 3026-3030
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    CNDO calculations of the excited states were performed on the first three members of paraffinic hydrocarbons—methane, ethane, and propane, and on three compounds of saturated three-membered rings—cyclopropane, ethylenimine, and ethylene oxide. The method gives a reasonable interpretation of the electronic spectra of both kinds of compounds.
  • Masuo Aizawa, Jun Mizuguchi, Shuichi Suzuki, Shoichi Hayashi, Teruo Su ...
    1972 Volume 45 Issue 10 Pages 3031-3034
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Electrochemical and dilatometric studies have indicated that at least three states of water exist in macromolecular gels. The properties of each state of water in gels such as agarose gels were investigated by highresolution and broadline PMR over the temperature range from +50 to −60°C. The linewidth of water protons in gels was found to depend markedly on the water content of gels, and the linewidth vs. water content curve gave two inflection points. One of the inflection points can be attributed to the so-called bound water, but the other cannot be explained unless three states of water are assumed in gels. Three kinds of transition temperatures were confirmed by anomalous changes in the PMR linewidth below 0°C. The so-called bound water exhibited no transition temperature between 0 and −20°C, and free water gave the transition temperature at 0°C. Moreover, the transition temperature of a quantity of water was distributed in the range from 0 to −20°C. On the basis of the transition temperature, the properties of water in macromolecular gels are discussed.
  • Masaru Ohsaku, Yuji Shiro, Hiromu Murata
    1972 Volume 45 Issue 10 Pages 3035-3048
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    (Methylthio)methanethiol, CH3SCH2SH, and (methylthio)methanethiol-d1, CH3SCH2SD, were prepared, and their infrared spectra were obtained in the gaseous, liquid, and solid states. The obtained spectra have been assigned. The frequency shifts by D-substitution, gaseous-liquid transition, and liquid-solid transition have also been discussed. The normal coordinates of these thiols have been treated by a modified Urey-Bradley force field. The force constants used in the computation have been transferred from those previously reported, but we adjusted them to produce the experimental wave numbers. The calculated wave numbers correspond well with those observed. The stable molecular conformations of the normal and deuterated species have been determined by the aid of the normal coordinate treatment. In the gaseous and liquid states, at least three to four forms from among TT, TG, GT, GG, and GG′ have been confirmed to exist. In the solid state, though, CH3SCH2SH or GH3SCH2SD exists in only one form: GG.
  • Hiroshi Yoneyama, Hideo Tamura
    1972 Volume 45 Issue 10 Pages 3048-3053
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electrochemical properties of lithiated nickel oxide were studied using a single-crystal (100) face and a sintered body. The IV curves of the Fe2+/Fe3+ system on the single-crystal electrode were almost the same as those on the sintered-body electrode when the electric resistivities of the crystals were equal. However, a high amount of charge was obtained at the sintered-body electrode compared with the single-crystal electrode when the crystals were oxidized anodically. The effect on these reaction rates of the space charge depletion layer formed on the electrode surface will be discussed. The dependence of the reaction rates on the electric resistivity of the crystal can be understood to a certain extent through this discussion.
  • Reizo Dohno, Takatugu Azumi, Shiro Takashima
    1972 Volume 45 Issue 10 Pages 3054-3058
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The preparation of non-permselective membrane for the divalent cation was attempted by coating it with thin vinylon film on one side of a commercial cation-exchange membrane. When the coating surface of the cationexchange membrane was set on the concentration-compartment side (cathode side), the permselectivity coefficient of the calcium ion to the sodium ion was equal to that of untreated cation-exchange membrane and no effect of the selective treatment was recognized. However, when the coating sufrace was directed to the desalting-compartment side (anode side), an effect of the selective treatment was observed; in this case, the permeability of the calcium ion was more depressed, corresponding with the formalation degree of the selective-treatment membrane; for example, the permselectivity of the calcium ion for the membrane which was formalated for 180 min at 30°C decreased about one half compared with the untreated membrane. The electric resistance of the cation-exchange membrane increased upon the coating with the vinylon film, and especially the resistance of the calcium ionic-form membrane indicated a remarkable increase.
  • Kunio Fukushima, Hiroko Yamamoto
    1972 Volume 45 Issue 10 Pages 3058-3064
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The normal coordinate treatment of optically active lattice vibrations of ammonium chloride and ammonium chloride-d4 at low temperature was made in order to elucidate the nature of the vibrations and obtain force constants in the potential in the crystals by the method of least squares. Using the constants, the optically active lattice vibrations of a crystal model for ammonium chloride and ammonium chloride-d4 at room temperature were calculated. The far-infrared spectra obtained and the Raman and infrared spectra in literature were discussed.
  • Yasumasa J. I’Haya, Toru Yunoki
    1972 Volume 45 Issue 10 Pages 3065-3067
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Ultraviolet absorption spectra, induced optical rotatory dispersion and circular dichroism of pyrene, TCNNQ, and their molecular complex were measured in acetylcellulose film and solution. The Cotton effect corresponding to each absorption maximum of these systems appeared. A perturbation of excited states of these molecules and their complex due to an asymmetric environment of acetylcellulose might be of paramount importance in producing a non-zero rotational strength in the corresponding molecular absorption region. The second charge-transfer band was clearly detected in the differential optical rotatory dispersion spectrum of the TCNNQ-pyrene molecular complex embedded in an acetylcellulose film. The method was shown to be promising in detecting very weak and closely overlapped transitions in various molecules.
  • Hatsuho Uedaira
    1972 Volume 45 Issue 10 Pages 3068-3072
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Activity coefficients for the ternary system glycylglycine-urea-water were measured by the isopiestic vapor pressure method at 25°C. The activity coefficients of glycylglycine were lowered by urea. The lowering increased with increasing concentration of urea and with decreasing concentration of the amino acid. It was dependent on amino acid concentration to a greater extent than in the system α-amino-n-butyric acid–urea–water. The activity coefficients of urea were also decreased by glycylglycine. The free energy of the transfer of glycylglycine from water to urea solutions in various concentrations was calculated. The values obtained were combined with enthalpy data to yield −3.9 e. u. as the entropy value for the transfer from water to 6 M urea solution. Results have been interpreted to support the existence of interaction between urea and glycylglycine.
  • J. P. Shukla, S. G. Tandon
    1972 Volume 45 Issue 10 Pages 3073-3075
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The formation constants for the metal chelates of Mn(II), Ni(II), Zn(II), and Cu(II) with N-phenylbutyrohydroxamic acid have been determined in 50 volume per cent dioxane-water mixture following the Bjerrum-Calvin pH titration technique and maintaining the titration medium at a constant salt background (0.1 M KClO4) and a temperature 25±0.1°C. The formation constants found are logK1=9.68(Cu), 6.85(Zn), 6.67(Ni), 5.25(Mn), and logK2=8.58(Cu), 5.52(Zn), 5.21(Ni), and 4.09(Mn), the stability order being Mn<Ni<Cu>Zn.
  • Mikio Hoshino, Masao Koizumi
    1972 Volume 45 Issue 10 Pages 3075-3077
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The effect of the addition of ethanol (quencher of the reaction) on the photoreduction of p-aminobenzophenone (NH2BP) and dimethyl-p-aminobenzophenone in cyclohexane and in ether has been studied. The order of quencher participation for ethanol has been found to be two for the former and one for the latter. The results were interpreted to be due to the formation of intramolecular C–T state during excitation, promoted by the attachment of one ethanol (or ether) molecule to the NH2-group and one ethanol molecule to O=C of NH2BP.
  • Kuniko Takeyama, Tetsuzo Atoda
    1972 Volume 45 Issue 10 Pages 3078-3080
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Heat capacities of liquid antimony trichloride and tribromide saturated with their respective vapors were determined with an adiabatic calorimeter as follows: 35.2 cal K−1mol−1 in the range, 90–210°C, for trichloride, and 34.6 cal K−1mol−1 in the range, 130–270°C, for tribromide.
  • Tetsuo Shinohara, Takato Yamada, Noriyuki Takebayashi, Shun-ichi Hirak ...
    1972 Volume 45 Issue 10 Pages 3081-3083
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Kinetic studies of isotopic ligand-exchange reactions, [Ru(NH3)5X]2++X*−=[Ru(NH3)5X*]2++X, where X=Cl, Br, and I, have been made in aqueous solutions. The effects of the hydrogen- and halide-ion concentrations, and of the ionic strength of the aqueous solution on the exchange rate had not been observed under certain definite experimental conditions. The rate constants were determined to be 3.15×10−4 sec−1 for the chloro-pentaammine 3.63×10−4 sec−1 for the bromopentaammine, and 1.1×10−4 sec−1 for the iodopentaammine at 80°C. The energies of activation were 20 kcal/mol (chloropentaammine), 23 kcal/mol (bromopentaamine), and 30 kcal/mol (iodopentaammine). The reactions proceed through the following two steps:
    [Ru(NH3)5X]2++H2O→[Ru(NH3)5H2O]3++X
    [Ru(NH3)5H2O]3++X*−→[Ru(NH3)5X*]2++H2O
    The first step is regarded as the rate-determining one.
  • Yuki Fujii
    1972 Volume 45 Issue 10 Pages 3084-3092
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A series of mixed cobalt(III) complexes with the general formula of K[Co(baen) (amino acid anion)2]·nH2O (baen=dianion of N,N′-ethylenebis(acetylacetonimine); amino acid = glycine, β-alanine, L-alanine, D-alanine, D,L-alanine, L-valine, D-valine D,L-valine, L-leucine, L-isoleucine, and L-phenylalanine) were newly prepared from a reaction mixture of trans-N,N′-ethylenebis(acetylacetoniminato)diaquocobalt(II), [Co(baen)(H2O)2], and the amino acids. Also prepared were mixed cobalt(III) complexes having the general formula of [Co(baen)(X)2]-ClO4(X=glycine ethyl ester, L-alanine ethyl ester, L-leucine ethyl ester, L-phenylethylamine, D-phenylethylamine, and D,L-phenylethylamine). From the elemental analyses, and the IR and NMR spectra, the amino acid anions were found to coordinate as a unidentate ligand, and the structures of all the complexes were determined to be trans with respect to the two nitrogen atoms of the coordinated amino groups. The NMR spectral behavior of the complexes containing D,L-amino acid anions and D,L-phenylethylamine was well interpreted in terms of the existence of the following three species in a relative ratio of 1:2:1; [Co(baen)(L-form ligand)2]±n, [Co(baen)(L-form ligand)(D-form ligand)]±n, and [Co(baen)(D-form ligand)2]±n. A rapid intermolecular exchange reaction of the apical amino acid anion groups was newly found in water: [Co(baen)(A)2]+[Co(baen)-(B)2]\ ightleftharpoons2[Co(baen (A)(B)] (where A and B indicate the apical amino acid anions). Also found was a rapid exchange reaction of the apical amino acid anion groups between the complex and free amino acid anion. Strong support for the rapid inter molecular exchange reaction was obtained in a CD spectral study of them.
  • Kousaburo Ohashi
    1972 Volume 45 Issue 10 Pages 3093-3095
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An investigation of the Fe2+ reductions of Co(ox)(NH3)4+, Co(ox)(en)2+, Co(ox)(trien)+, Co(ox)(dip)2+, Co-(ox)2(en), and cis-Co(ox)2(NH3)2 has been carried out spectrophotometrically. The rate constants of Co(ox)N4+-type complexes increase in this order: Co(ox)(phen)2+>Co(ox)(dip)2+>Co(ox)(NH3)4+>Co(ox)(en)2+>Co(ox)-(trien)+, and these of Co(ox)2N2-type complexes, cis-Co(ox)2(NH3)2>Co(ox)2(en). The variation in reactivity is mainly ascribed to a change in the enthalpy of activation. The rate constants of Co(ox)(NH3)4+, Co(ox)(en)2+, cis-Co(ox)2(NH3)2, and Co(ox)33− increase with the values of the hal-wave potential of the polarographic reduction (CoIII→CoII) and with the decrease in the wave number of the maxima of the absorption spectra of the complexes.
  • Nobuhide Tatsumoto, Takayuki Sano, Tatsuya Yasunaga
    1972 Volume 45 Issue 10 Pages 3096-3100
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Second ultrasonic absorptions with relaxation frequencies of 26, 36, 53, and 70 MHz could be observed in 0.27, 0.47, 1.0, and 2.0 M cyclohexane solutions respectively of propionic acid at 20°C. The consideration of the variations in the sound absorption, the sound velocity, and the chemical shift with the concentration leads us to the conclusion that the relaxation is attributable to the perturbation of the equilibrium between the open dimer and the monomer of propionic acid. The backward rate constant in this reaction is estimated to be about 109 sec−1M−1.
  • Kiyoshi Kawasaki, Muraji Shibata
    1972 Volume 45 Issue 10 Pages 3100-3104
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The following ten complexes have been isolated from a reaction mixture of the [CoCO3(gly)2] ion and L-glutamate in the presence of active charcoal: mer-[Co(gly)2L-glutH] (two isomers), mer-Cogly(L-glutH)2], mer-Λ-[Co(L-glutH)3],fac-Λ and Δ-[Co(gly)2(L-glutH], fac-Λ and Δ-[Cogly(L-glutH)2], and fac-Λ and Δ-[Co(L-glutH)3]. These complexes have been characterized by various spectral data. The Δ/Λ ratios in the fac isomers have been estimated to be ca. 60/40, 68/32, and 75/25 for the bis(glycinato), bis(L–glutamato) and tris(L–glutamato) complexes respectively, while no appreciable stereoselectivity has been found in the corresponding mer isomers.
  • Ryokichi Tsuchiya, Masatatsu Suzuki, Eishin Kyuno
    1972 Volume 45 Issue 10 Pages 3105-3109
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The deaquation-anation reaction of cis-[CoX(H2O)N4]Y2 type complexes, where X is chloride or bromide ion, N4 is tetraammine or bis(ethylenediamine), and Y is chloride, bromide or nitrate ion, was investigated by means of both derivatographic and isothermal methods. Some of these reactions were found to include the stereochemical changes, the structure of reaction products formed by deaquation-anation reaction being considerably affected by the counter ionic species: the chloride complexes, where Y=Cl, were deaquated with retention of cis-structure, whereas the bromide complexes, where Y=Br, underwent cis-to-trans stereochemical change. According to the isothermal measurement in the isomerization of cis-[CoCl(H2O)en2]Br2·H2O, cis-[CoCl(H2O)en2]-Br(NO3) and cis-[CoBr(H2O)en2]Br2·H2O, these rates were found to obey the first-order rate law and the activation energies, Ea, were obtained to be 38±5, 68±6 and 37±5 kcal mol−1 and the enthalpy changes, ΔH, 13.5±2.0, 7.5±2.0 and 13.3±2.0 kcal mol−1 for the respective complexes.
  • Akio Yamamoto, Shigeo Go, Masaharu Ookawa, Mitsuaki Takahashi, Sakuji ...
    1972 Volume 45 Issue 10 Pages 3110-3117
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetics and stoichiometry of nitrogen fixation with TiCl3-Mg and VCl3-Mg in tetrahydrofuran (THF) systems were studied. The systems react with molecular nitrogen at room temperature and normal pressure giving magnesium dichloride and nitrogen-containing complexes of compositions [MNMg2Cl2(THF)], where M=Ti and V, according to the stoichiometry: MCl3(THF)3+\frac52Mg+\frac12N2→[MNMg2Cl2(THF)]+\frac12MgCl2(THF)2. Properties of the isolated nitrogen-containing complexes were examined. Reactions under argon and hydrogen gave hydride-containing complexes. The initial rate of nitrogen fixation was first order with respect to the amounts of MCL3, Mg, and nitrogen pressure. A mechanism involving the complexation of N2 with dimeric M(II) species followed by rate-determining process to react with magnesium is proposed and discussed.
  • Kazuhiko Hotta, Teruo Kubomatsu
    1972 Volume 45 Issue 10 Pages 3118-3121
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Kinetic studies were carried out on the hydrogenation of the α,β-unsaturated aldehyde, 2-methyl-2-pentenal (UD), over the Raney cobalt catalyst modified with various amounts of Co-, Mn-, Ni- and PdCl2 in n-hexane under atmospheric pressure at 40 and 20°C. Initial rates of formation of the saturated aldehyde (rSD), saturated alcohol(rSA) and unsaturated alcohol(rUA) were determined in the concentration range of UD((CUD) 0.018–0.263 mol/l. It was found that (rSD+rSA) obeyed a Langmuir-type rate equation and rUA a different one. The rate equations are as follows.
    rSD+rSA=\frack1·b1·CUD(1+b1·CUD)2, rUA=\frack2·b2·CUD(1+b2·CUD)2
    where k and b denote the rate constant of the surface reaction and parameter for the adsorption of UD and hydrogen, respectively, the subscripts 1 and 2 representing the formation of SA and SD and that of UA, respectively. Kinetic parameters k1, k2, b1 and b2 were found to vary with the amount and kind of modifier. The variation of b1 and b2 was irregular. The rate constant k1 decreased with increasing amount of Co-, Mn- and NiCl2 added; it increased remarkably with the addition of PdCl2. The variation of k2 was more complicated. Addition of a small amount of the modifiers did not decrease k2. Further addition of Co- and MnCl2 made k2 decrease, while that of NiCl2 made it increase. Mechanism of the modification with these metal chlorides is discussed on the basis of the active site hypothesis.
  • Yoshihiro Nagao, Kensuke Shima, Hiroshi Sakurai
    1972 Volume 45 Issue 10 Pages 3122-3126
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Irradiation of ethoxycarbonylmethyltriphenylphosphonium salts (IV) gave products expected to be derived from the homolytic fission of the P–CH2CO2Et or P–Ph bond. The rate of the product formation was dependent strongly on the anion species and on the solvent polarity; an oxidizable anion was effective for the photolysis and the less polar the solvent the faster the rate became. It was found through the measurement of the electrical conductance that the degree of electrolytic dissociation of IV was very low at the concentration employed in the photolysis. On the basis of these results, the photolysis of IV was confirmed to proceed through a direct charge transfer from an anion to a cation.
  • Yoshitane Kojima, Kimiko Usui, Shinichi Kawaguchi
    1972 Volume 45 Issue 10 Pages 3127-3130
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Because of a long induction period, the reaction between acetone and copper(II) bromide does not occur readily in pure DMF. However, in the presence of an acid, it proceeds readily. The initial rate is proportional to the product of the concentration of acetone and perchloric acid, but independent of the concentration of copper(II) bromide. The acid-catalyzed bromination of acetone by bromine has also been studied in DMF and found to obey the same second-order rate law as that in water. Both bromination reactions of acetone in DMF by copper(II) bromide and bromine were interpreted to be controlled by the enolization process of acetone.
  • Takao Kawaki, Harukichi Hashimoto
    1972 Volume 45 Issue 10 Pages 3130-3132
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Cuprous acetate was prepared from phenylcopper and acetic acid, and its reactivity for organic halides was investigated. The mixed anhydrides containing an acetyl group are formed easily from cuprous acetate and acyl halides. The reaction of cuprous acetate with CH3I, C2H5I, CH2=CHCH2Br, and PhCH2Cl in acetonitrile gives the corresponding ester. The addition of ethylenediamine converts the above reaction to a reductive coupling reaction, resulting in bibenzyl (50% yield) from benzyl chloride and 1,5-hexadiene (95–98% yield) from allyl chloride or bromide. The reaction of cuprous acetate-ethylenediamine with aryl bromide or iodide in DMF gives a reductively dehalogenated product, i.e., the corresponding hydrocarbon, in a small yield.
  • Norio Maeno, Takeshi Itagaki, Seiichi Uno, Kohji Matsui
    1972 Volume 45 Issue 10 Pages 3133-3139
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Several 4- or 5-substituted O-(s-triazinyl)-2-aminophenols were synthesized, and the kinetics of the Smiles rearrangement of these compounds have been studied spectrophotometrically in methanol, ethanol, and 2-propanol in order to make clear the effects of substituents on the rearrangement. Substituents in the s-triazine nucleus were found to affect the progress of the reaction to a great extent by changing the positive character of the triazine-ring carbon. On the other hand, a substituent in the aminophenol moiety affects both the nucleophilic reactivity of the attacking amino group and the stability of the leaving phenoxide anion or the reactivity of the s-triazinyl group, but the effect on the amino group was found to be predominant, the effect of a substituent in the aminophenol moiety was smaller than that of the substituents in the s-triazine nucleus.
  • Kenji Nakamura, Noboru Nohara, Kohji Matsui
    1972 Volume 45 Issue 10 Pages 3140-3147
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Several 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N1-(dimethoxy-s-triazinyl)-o-phenylenediamines were synthesized, and the migrations of the s-triazinyl group were investigated in these compounds. In methanol, every 4-substituted N1,N1-bis(s-triazinyl)-o-phenylenediamine gave only 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N2-(dimethoxy-s-triazinyl)-o-phenylenediamine by the migration of the dimethoxy-s-triazinyl group; the rearrangement was assumed to proceed through an intramolecular nucleophilic attack by the ortho amino group upon the ring carbon of the dimethoxy-s-triazinyl group. However, in the presence of a small amount of acid, the N1N2 migration of the bis(diethylamino)-s-triazinyl group occurred preferentially, and two kinds of rearranged products were obtained. The kinetics of the rearrangement have also been studied spectrophotometrically in methanol, and the effects of the substituents on the rearrangement have been discussed.
  • Juntaro Tanaka, Takao Katagiri, Kunihiko Takabe, Tadashi Sakamoto
    1972 Volume 45 Issue 10 Pages 3147-3149
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    1,1-Dimethylcyclopropane(I) was found to dimerize selectively by the action of boron trifluoride etherate. In the products, compound (III), which had been presumed, and the reaction intermediates (VII and VIII) were identified. The reaction mechanism was discussed. 1,2-Dimethylcyclopropane(VI) gave the same products.
  • Mitsuaki Narita, Takero Teramoto, Makoto Okawara
    1972 Volume 45 Issue 10 Pages 3149-3155
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to achieve solid-phase acyl activation of carboxylic acid, the syntheses and reactions of polymers containing hydroxamic acid and N-hydroxysuccinimide residues were investigated. A polymer containing hydroxamic acid residue was obtained by the modification of cross-linked copolymer of p-nitrophenyl acrylate with styrene, and one containing N-hydroxysuccinimide residue was prepared by copolymerization of N-acetoxymaleimide with styrene followed by hydrolysis. These N-hydroxy polymers were allowed to react with N-protected amino acids by means of the dicyclohexylcarbodiimide method giving the activated polymer ester. While the polymer containing hydroxamic acid residue was inferior to that containing N-hydroxysuccinimide residue in activation of carboxylic acid, amino acid esters of the latter were active enough to react with another amino acid to yield dipeptides almost quantitatively without racemization.
  • Takashi Matsumoto, Y\={u}kei Hosoda, Kiyomi M\={o}ri, Kenji Fukui
    1972 Volume 45 Issue 10 Pages 3156-3160
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Reformatsky reaction of 2-phenylpropanal (I) with methyl α-bromopropionate gave the diastereomeric methyl 3-hydroxy-2-methyl-4-phenylvalerates, IIa, IIb, IIe, and IId, in a 5 : 24 : 16 : 55 ratio. The configurations of these β-hydroxy esters were assigned by the following experiments. The reduction of IIa–IId with LiAlH4 gave the corresponding diols, IIIa–IIId, which were then converted to the monotosylates, IVa–IVd. The further reduction of IVa or IVc and IVb or IVd with LiAlH4 gave the epimeric 2-methyl-4-phenyl-3-pentanols, V and VI respectively. Since V and VI were also obtained as minor and major products (20 : 80 ratio) of the Grignard reaction of I with isopropylmagnesium iodide, the configurations of the C-3 and C-4 positions in IIa–IId were assigned. The Wittig reaction of I with carbomethoxyethylidenetriphenylphosphorane gave methyl 2-methyl-4-phenyl-2-cis-pentenoate (VII) and its trans-isomer (VIII), which were then reduced to the corresponding alcohols, IX and X respectively. The cis-hydration of IX gave IIIc and IIId, while a similar treatment of X gave IIIa and IIIb. From this experiments, the relative configurations from the C-2 position to the C-3 position in IIa–IId were also assigned. These configurational assignments of IIa–IId were further confirmed by the ozonization of IIa–IId.
  • Kuniyuki Tomita, Norio Yoshida
    1972 Volume 45 Issue 10 Pages 3160-3164
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Oxidation of 3-alkoxycarbonyl-substituted pyrrolic compounds with aqueous potassium ferricyanide in the presence of potassium hydroxide afforded 2,2′- and 5,5′-bispyrrolenine derivatives, which were in equilibrium with each other in solution via radical intermediates. The substituent effects on the dimer formation will also be discussed in connection with the characters of the intermediate pyrryl radicals.
  • Yasuhiko Kato, Takashi Kuboyama, Ichiro Hirao
    1972 Volume 45 Issue 10 Pages 3165-3169
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In continuing a previous report concerning the syntheses and steric configurations of 3-(5-nitro-2-furyl)-2-(2-furyl)acrylic acid derivatives, trans and cis 3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile and their related compounds have been synthesized. The isomerization was involved in the conversion of cis-3-(5-nitro-2-furyl)-2-(2-furyl)acrylamide (I) to trans-3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile (II) upon the treatment of phosphoryl chloride. II was converted to its cis isomer (III) by treating it with hydroxylamine, hydrazine hydrate, or hydrochloric acid. II and III were treated with bromine at 5–10°C in carbon tetrachloride to afford dibromo compounds, (3S : 5S and 3R : 5R)-(IV) and (3S : 5R and 3R : 5S)-3-(5-nitro-2-furyl)-3-bromo-2-(5-bromo-2,5-dihydro-2-furylidene)propionitrile (V) respectively. When the bromination was carried out at a higher temperature (70–73°C), a monobromo compound, cis-3-(5-nitro-2-furyl)-2-(5-bromo-2-furyl)acrylonitrile (VI), was obtained from both II and III. VI was also produced by heating IV or V in refluxing acetone. The structures and configurations of these compounds were discussed on the basis of their experimental and spectral data.
  • Toshifumi Hirata
    1972 Volume 45 Issue 10 Pages 3169-3171
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The chemical shifts of methyl protons of a number of bicyclo[3.1.1]heptanols and their acetates were measured on carbon tetrachloride and benzene in order to examine the correlation between the benzene-induced shifts and the spatial arrangements of the functional groups concerned. Thus, the shifts induced by benzene were found to be useful in establishing both the location and the stereochemistry of methyl protons situated in the vicinity of the hydroxyl or the acetoxyl function in a pinane skeleton.
  • Norio Yoshino, Takeshi Yoshino
    1972 Volume 45 Issue 10 Pages 3172-3174
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reactions of n-butoxytitanium chloride, TiCln(OnBu)4−n (n=0,1,2,3,4), with 1,4-dioxane, tetrahydrofuran, and tetrahydropyran have been studied. No adducts have been isolated when n=0,1,but the compounds TiCl2-(OnBu)2·O(CH2CH2)2O, TiCl2(OnBu)2·C4H8O, TiCl2(OnBu)2·C5H10O, TiCl3(OnBu)·O(CH2CH2)2O, TiCl3(OnBu)·2C4H8O, TiCl3(OnBu)·2C5H10O, TiCl4·O(CH2CH2)2O, TiCl4·2C4H8O and TiCl4·2C5H10O have been isolated when n=2,3,4. Possible structures for these adducts were discussed on the basis of elemental analysis, IR spectra, NMR spectra, and molecular weights. The adducts undergo hydrolysis very quickly with moisture.
  • Yukio Sugimura, Nobuo Soma, Yukichi Kishida
    1972 Volume 45 Issue 10 Pages 3174-3178
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Phenacylpyridinium ylide (2) reacted with tropone (1) to afford 2-hydroxy-2-phenyl-3-phenacyl-2H-cyclohepta[b]furan (3) which was converted into 2-(1′,2′-dibenzoylethyl)tropone (4). The reactions of tropone with several kinds of pyridinium bromides (7) yielded 2-substituted tropones in the presence of amine, and 1-azaazulene derivatives (9, 10, 11) in a one-step formation in the presence of ammonium acetate.
  • Seizo Tamagaki, Keishi Sakaki, Shigeru Oae
    1972 Volume 45 Issue 10 Pages 3179-3182
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The mechanism of deoxygenation reaction of oxaziridine with trivalent phosphine was kinetically examined by changing substituents, solvents, and temperatures. The reaction proceeds through an attack of phosphine on oxgen in a concerted manner rather than on nitrogen or carbon, eventually producing the corresponding imine and phosphine oxide. The mechanism of the title reaction was compared with those of similar deoxygenations of epoxide and thioepoxide.
  • Yasuhira Takeuchi, Shuzo Akiyama, Masazumi Nakagawa
    1972 Volume 45 Issue 10 Pages 3183-3187
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Syntheses of α,ω-di-1-anthrylpolyenes have been carried out by the Wittig reaction for information on the role of aromatic terminal groups on the electronic spectral regularity of α,ω-diarylpolyenes. The reaction of phosphoranes derived from 1-anthrylmethyl-, 3-(l-anthryl)propenyl-, and 5-(1-anthryl)-pentadienyltriphenylphosphonium bromides with 1-formylanthracene, 3-(1-anthyrl)propenal, 5-(1-anthryl)pentadienal, and muconic aldehyde afforded a series of di-1-anthrylpolyenes (I1−6) by a proper combination of the phosphorane and the aldehyde moiety. Owing to the broading of absorption bands in the long wavelength region, no discussion could be made on the electronic spectral regularity.
  • Otohiko Tsuge, Akiyoshi Torii
    1972 Volume 45 Issue 10 Pages 3187-3191
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In the presence of hydrochloric acid, 9-vinylacridine reacts with nitrosobenzenes having electron-donating groups such as p-nitroso-N,N-dialkylaminoaniline and p-methylnitrosobenzene to yield a four-membered oxazetidine, as the first example of a non-fluorinated oxazetidine ring system. A new 2:2 adduct, to which the perhydro-1,2,7-oxadiazepine structure is assigned tentatively, is formed in the reaction of 9-vinylacridine with nitrosobenzene or p-chloronitrosobenzene under similar conditions.
feedback
Top